Linear phosphonitriles



United States Patent 3,467,704 LINEAR PHOSPHONITRILES Edward F. Moran,Wenonah, and Donald P. ,Reider, Woodbury, N.J., assignors to E. I. duPont de Nemours and Company, Wilmington, Del., a corporation of DelawareNo Drawing. Filed Aug. 24, 1966, Ser. No. 574,549 Int. Cl. C08g 33/16US. Cl. 260-551 Claims The present invention relates to novelphosphorusnitrogen compounds and processes for their preparation. Moreparticularly, the invention relates to linear organic substitutedphosphonitriles represented by the formula:

wherein the Rs represent monocyclic aryl radicals, X is an amino radicalwhen n equals 1 or 2 or a monocyclic aryl radical when n equals 2,phosphonitrilic compounds of increased chain length and phosphonitrilicphosphine oxides represented by the formula:

wherein the Rs have the designation given above, and processes for theirpreparation.

In recent years, considerable attention has been focused on theso-called inorganic polymers and in particular, on phosphonitrilicchlorides and related compounds. Whereas efforts to prepare cyclicphosphonitriles have enjoyed some measure of success (US. 3,260,685,3,230,- 252; British 1,023,415, 1,017,375, 1,013,462), the efforts toprepare the linear analogs have met with little success. Only very shortchain linear phosphonitriles and related compounds have been preparedand most often, by methods which have serious drawbacks from, forexample, an economic or safety standpoint. Triarylphosphinimidechlorides, intermediates in the above process, have been prepared by thereaction of a triarylphosphine with chloramine, as described in theJournal of the American Chemical Society, vol. 81, page 2983 (1959) andParticle, vol. 3, page 25 (1960). However, the use of chloramine as areactant in the process is disadvantageous because, among other things,it must be generated separately and it is both unstable and somewhattreacherous. As described in Particle, the reaction of chlorine andammonia to form chloramine is highly exothermic, producing flames andtemperatures of about 600 C.

Furthermore, in the preparation from phosphine oxides, the art describesmethods wherein sodium azide must be used in processes for makingphosphonitrilic oxides, one such method is described in the Journal ofthe American Chemical Society, vol. 83, page 4466 (1961). The use ofazides presents a serious safety problem due to the fact that they areboth explosive and poisonous. The method of the present invention avoidsthe use of azides and thus provides a safer and more economical methodfor obtaining phosphonitrilic phosphine oxides.

It has now been discovered that novel long chain linear phosphonitrilesof the formula trivalent or pentavalent chlorophosphines of the formula(R )(R )PCl wherein the Rs represent monocyclic aryl radicals and m is 1or 3 in presence of base,

(c) ammoniating the resulting product to produce the linearphosphonitrile designated above, with the proviso that when 1711 equas lin the above formula the reaction product of step (b) is chlorinatedprior to ammoniation.

Furthermore, the chain length of the monocyclic aryl substituted linearphosphonitrile of the formula prepared as described above can beincreased by reacting it with a disubstituted trivalent or pentavalentchlorophosphine of the formula (R (R )PCl as designated above, where mis 1 or 3 in the presence of base and ammoniating the resulting productsto produce a higher molecular weight linear phosphonitrile of theformula wherein the Rs represent monocyclic aryl radicals.

As stated above, phosphonitrilic phosphine oxides of the formula:

wherein the Rs are monocyclic aryl radicals can also be prepared. Theprocess for their preparation involves carrying out the proceduredescribed hereinabove in step (a) and step (b) with the proviso that ifthe phosphinimide chloride is reacted with a disubstituted trivalentchlorophosphine, the product be chlorinated and then hydrolyzing theresuting phosphonitrile compound having the structure (R) (R (R )P:NP(R)(R (CD Upon hydrolysis oxygen replaces the chlorine atoms of thephosphonitrile and the corresponding phosphonitrilic phosphine oxiderepresented above is produced.

The novel linear monocyclic aryl substituted phosphonitriles of thepresent invention are thermally and hydrolytically stable compounds. Asthermally stable (e.g., stable when heated up to about 400 C.) andhydrolytically stable (e.g. unchanged by contact with boiling water)materials, the compounds of the present invention are useful as heattransfer media, high temperature lubricants and hydraulic fluids. Inaddition, the linear phosphonitriles of the formula (R) [P(R )(R)=N],,P(R (R )NH Cl Where n equals 1 or 2, are useful chemicalintermediates in that each phosphonitrile may serve as the startingmaterial for the reaction with a chlorophospine and subsequentammoniation as described herein to produce the next higher homologue inthe series.

The phosphonitrilic phosphine oxide as described above wherein the Rsare phenyl radicals has been characterized in Journal of OrganicChemistry, vol. 30, p. 3861 (1965) as a compound stable to hydrolysis byvarious agents and thermally stable after 16 hours at 250 C. and then 5hours at 280 C. in an evacuated, sealed tube. It has also beendiscovered in the present invention that the said oxide is stable athigher temperatures, i.e., the oxide is recovered unchanged after 16hours at 310 C. in an evacuated, sealed tube. The phosphine oxides areuseful in high temperature applications as described above.

In a preferred embodiment of the invention for the preparation of (C5H5)where when n equals 1, X is an amino radical and when n equals 2, X is aphenyl radical, chlorine gas is passed into a solution oftriphenylphosphine in an inert solvent, such as chloroform, to producetriphenylchlorophosphine. This reaction can be conducted at temperaturesof from about 20 C. to 50 C. Preferably, the reaction is carried out inan ice bath at temperatures ranging from about 10 to 5 C. Chlorine gasis passed into the solution, usually until the colorless solution turnssharply to a dark yellow color due to excess chlorine gas. The colorchange is indicative of complete formation of triphenyldichlorophosphine. Preferably, anhydrous ammonia is passed into thechlorophosphine solution until the yellow color disappears and a heavywhite precipitate forms. This reaction is exothermic and, therefore,generally no external heating is required. The temperature usuallyvaries from about to 65 C. Upon addition of at least a slight excess ofammonia, the reaction is complete, and generally there is a drop intemperature.

The triphenylphosphinimide chloride is subsequently reacted with eithera trivalent or pentavalent disubstituted chlorophosphine represented bythe formula wherein the Rs are monocyclic aryls, e.g., phenyl andsubstituted phenyl and m equals 1 or 3, egg. (C H PCl in the presence ofbase, preferably a Lewis-type base, e.-g. triethylamine. As used herein,a Lewis base is defined as a compound capable of giving up to an acid anunshared pair of electrons. While the present invention is not intendedto be limited by theory, it is believed that the Lewis base, e.g,triethylamine, acts as an HCl acceptor (i.e. HCl is split off in thereaction:

and forms a salt, e.g. an amine salt such as Et N-HCl. Examples ofsuitable Lewis bases that can be used in the present invention aretertiary amines, e.g., trimethylamine, triethylamine, tributylamine, andpyridine. In view of the fact that chlorophosphines are easilyhydrolyzed to the corresponding acids, it is desirable to conduct thereaction under anhydrous conditions. When this reaction is conductedwith a pentavalent trichlorophosphine the resulting product is [(R) (R)(R )P=NP(R )(R (CD 1, the Rs being monocyclic aryl radicals, e.g.,phenyl and substituted phenyl. The resulting chlorine-containingphosphonitrile is ammoniated with anhydrous ammonia to produce thecorresponding linear monocyclic aryl substituted phosphonitrile. In asimilar fashion, but, when the reaction is carried out with a trivalentchlorophosphine, e.g. (C H PCl, the resulting phosphonitrile does notcontain chlorine and has the formula:

wherein the Rs represent monocyclic aryl radicals, e.g., phenyl orsubstituted phenyl radicals. Therefore, it is necessary to firstchlorinate the intermediate prior to ammoniation, so that the compoundreacted with ammonia has the formula The ammoniation of the mixture asdescribed above results in the formation of linear phosphonitrileshaving the formula wherein the Rs represent monocyclic aryl radicals,and when n equals 1 or 2, X is amino radical and when n equals 2, X is amonocyclic aryl radical. Monocyclic aryl radicals are, for example,phenyl and substituted phenyl radicals of the formula (C H ,,)Y where Yrepresents, for example, an alkyl of from 1 to 6 carbon atoms, such asmethyl, propyl, hexyl; alkoxy of from 1 to 6 carbon atoms such asmethoxy, propoxy, hexoxy; perfiuoroalkyl having 1 to 4 carbon atoms inthe alkyl group such as perfiuoromethyl, perfluorobutyl; perfluoroalkoxyhaving 1 to 4 carbon atoms in the alkoxy group such as perfluoromethoxy,perfluorobutoxy; fluoro; nitro; cyano and n has a value of from 1 to 5.

In the reaction of a trisubstituted phosphine with a chlorinatin gagent, at least one mole of chlorine is required for each mole of saidphosphine. A slight excess of chlorine is usually employed to insurecomplete formation of the chlorophosphine. The formation of a darkyellow color in the reaction vessel indicates excess chlorine has beenadded and that the reaction is completed. At least two moles ofammoniating agent are required for each mole of chlorophosphine, andgenerally, a slight excess of ammonia is employed. In this reaction,ammonium chloride is also produced in equal amounts with the desiredphosphinimide chloride and the formation of a heavy white precipitate,viz. ammonium chloride, is indicative of a complete reaction.

The reaction of a phosphinim-ide chloride with either a disubstitutedtrivalent or pentavalent chlorophosphine requires only about equimolaramounts of reactants. However, an excess of about one to two moles ofthe phosphinimide chloride can be used. For exam le, in the preparationof (C H P=NP(C H =NP(C H Cl, the use of excess, e.g. about one mole, ofthe phosphinimide chloride, gives somewhat higher yields. A largeexcess, e.g., more than about 2 moles, of the phosphinimide chloridedoes not provide any additional advantage. The amount of the ammoniatingagent employed that is reacted with the solution of thechlorine-containing phosphonitrilic intermediate to produce the desiredlinear chlorine-containing phosphonitriles ranges from at least twomoles of ammonia per mole of intermediate to a reasonable excess ofammonia. The reaction is carried out in the presence of a Lewis base asdescribed above. The amount of the base, e.g. triethylamine, employedcan be from about at least 2 moles to about 6 moles. It appears that theamount of base used in the reaction determines the specific finalproduct. For example, the use of excess triethylamine in amounts of 4 ormore moles results in the completely monocyclic aryl substitutedphosphonitrile, (C H P=NP(C H ==NP(C H C1 as the major product and minoramounts of (cal I5 (C H5 whereas on the other hand, the use of less than4 moles, eg about 2 moles, results in the formation of as the majorproduct.

The reaction of the trisubstituted phosphinimide chloride with thedisubstituted trivalent or pentavalent chlorophosphine is preferablycarried out in an inert organic solvent. The mixture of the reactants insuch a solvent is refluxed, at temperatures of about 40 to 120 C.,preferably about 60 to C., for periods of :at least 15 minutes up to 3or 4 hours, preferably about 1 to 2 hours. After cooling to about 10 to15 C., the solution is chlorinated if a disubstituted trivalentchlorophosphine is the initial reactant, and then ammoniated by treatingwith ammonia, heated rapidly to reflux for several minutes, and thencooled to recover the products.

In place of ammoniation as described above, the phosphonitrilicintermediate, (C H P=NP(C H (CD may be subjected to hydrolysis to formthe corresponding phosphonitrilic phosphine oxide,

( s s 3 s s 2 as previously stated. The hydrolysis may be carried outusing any known conventional methods which will add at least one mole ofwater for each mole of the intermediate, (C H P=NP(C H Cl present, forexample, simple evaporation of the compound from the reaction solventover a steam bath may suflice for small scale preparations. Likewise,the direct addition of water or a water-organic solvent mixture, e.g.water-dioxane, to a solution of the intermediate and subsequentevaporation yields the phosphonitrilic phosphine oxide.

The reactions described above are generally, but not necessarily,carried out in the presence of an inert organic solvent which acts asthe reaction medium. Any inert organic solvent may be used in theprocess, for example, non-polar hydrocarbons or halogenated hydrocarbonswhich are chemically inert to the reactants, such as 6 to 12 carbon atomalkanes, 1 to 10 carbon atom halogenated alkanes, 1 to 6 carbon atomnitriles and aromatic halogenated hydrocarbons such as mono-, diandtrihalogenated benzenes. Specific examples of inert organic solventsinclude straight and branched chain isomers of hexane. octane anddecane, chloroform, carbon tetrachloride, dichloroethane,tetrachloroethylene, tetrachloroethane, acetonitrile, propionitrile,chlorobenzene, o-dichlorobenzene and trichlorobenzenes. The .amount ofsolvent used can vary considerably and, when used, the minimum amount isthat which facilitates stirring.

The reaction product (C H P=NP(C H =NH Cl, made according to theprocedure described above can be further treated to increase the chainlength of the chlorinecontaining phosphonitrile, namely, to prepare e s3P:NP s s 2 s s) F z by repeating the steps involving treatment with thechlorophosphine and ammoniation. The reaction conditions required toproduce the compound where n equals 2 are substantially the same asthose already described for the compound where n equals 1.(C6H5)3P:NP(C6H5)2:NH2C]. iS reacted in abut q11imolar amounts with adisubstituted trivalent or pentavalent chlorophosphine of the formula (R)(R*)PCl as previously described in the presence of base, e.g., at leasttwo moles of a Lewis base, such as triethylamine and preferably, aninert solvent as previously described as the reaction medium. If thetrivalent chlorophosphine is used, the resulting intermediate, e.g.

(CGHE) 3 e s 2 s s) 2 must be chlorinated, e.g. treated with at leastone mole of chlorine to produce the corresponding pentavalentintermediate (C H P=NP (C H =NP(C H Cl which is subsequently ammoniated,e.g. treated with at least tWo moles of ammonia, as previouslydescribed.

The following examples illustrate the preparation of the novelcompositions of this invention and processes for their preparation.However, the examples are intended to be illustrative only and are notto be construed as limiting the invention in any way. The partsmentioned in the examples are parts by weight unless otherwisespecified.

EXAMPLE 1 Step 1 The chloroform used as the solvent in this step waswashed three times with 92 parts of concentrated H 50 per 1500 parts ofsolvent and then washed thoroughly with water. Calcium hydride is addedto the chloroform and the mixture stirred overnight. Chloroform is thendistilled OE and kept under a N atmosphere.

In a 1000 ml. flask fitted with a condenser, 131 parts of (C H P isdissolved in 2978 parts of CHClg by stirring under a stream of N Theflask is then immersed in an ice bath and chlorine gas is passed intothe solution until the solution turns dark yellow and excess chlorineappears in the condenser. Nitrogen is used to drive off the excesschlorine and anhydrous ammonia is then passed into the solution at roomtemperature. The reaction is exothermic and the temperature reaches theboiling point of chloroform (about 61 C.). The addition of NH iscontinued until the yellow color of the solution disappears and a heavywhite precipitate forms. The solution is refluxed for 30 minutes, thenhot filtered to remove NH Cl. 1416 parts of dry ether is added to thefiltrate. On cooling, a crystalline precipitate forms which, is filteredand Washed with ether to give 149 parts (95% yield) of (C H PNH Cl, M.P.233-235 C. The infrared spectrum agrees with that reported in theliterature.

Analysis.-Calcd. for C H PNCl: C, 68.90%; H,

6 5.42%; N, 4.46%; P, 9.89%; Cl, 11.32%. Found: C. 68.25% H, 5.53%; N,4.60%; P, 9.78%; Cl. 10.31%.

Steps 2 and 3 Into a 1000 ml., three-necked flask with a thermometerwell, is placed 82 parts of (C H PNH Cl, made according to the proceduredescribed above, and 76 parts of (C H PCl All weighings and transfersare done in a Glove Bag under nitrogen. Under a stream of nitrogen,about 1566 parts of the solvent acetonitrile is distilled into the flaskfrom calcium hydride. The flask is then fitted with a mechanicalstirrer, thermometer, reflux condenser, and a funnel containing 53 partsof (C H N. The mixture is heated to reflux (about 84 C.) and the (C H Nadded rapidly. After refluxing for 30 minutes, the mixture is cooled to15 C. and 9 parts of NH is passed in through the joint previously usedfor the dropping funnel. When the addition of NH is complete, HCl ispassed through the mixture to insure that the hydrochloride of theproduct is formed. The reaction mixture is filtered to give parts ofsolid which are then slurried in hot isopropanol to give 55 parts ofsolids identified as NH Cl and, on evaporation of the solvent, 10 partsof (C H NHCl. The filtrate from the original reaction is concentrated byevaporation on a steam bath to give a resinous solid material. Slurryingthe solid in benzene produces crystals which are recrystallized twicefrom acetone to give parts (60% yield) of M.P. 245247 C. The phosphorusNMR spectrum gives two peaks of equal intensity with chemical shifts at-21.6 and 19.6 ppm. The P=NP- band appears as a triplet at 1280-1320 cm?in the IR spectrum. The proton NMR gives a proton ratio determined to be13/1 (theoretical 12.5/1).

Analysis.-Calcd. for C30H27P2N2C11 C, H, 5.30%; N, 5.47%; P, 12.10%; Cl,6.93%. Found: C, 69.93%; H, 5.30%; N, 5.35%; P, 12.07%; Cl. 6.55%.

EXAMPLE 2 The process described in Example 1 is repeated with theexception that in Step 2 a trivalent chlorophosphine is reacted with thephosphinimide chloride. Accordingly, the reaction is between 31 parts of(C H PNH Cl and 25 parts of (C H PCl in 800 parts of chloroform and inthe presence of 20 parts of (C H N. After refluxing the mixture forabout 30 minutes, the mixture is cooled and contacted with chlorine gasunder a stream of nitro' gen until the solution turns yellow indicatingexcess chlorine is present. The excess chlorine is drawn off undervacuum and excess ammonia (about 5 parts) is added at room temperature.A solid identified as NH Cl is filtered from the resulting solution in aclosed system. After adding excess ether and allowing the filtrate tostand overnight, crystals separate out and 17 parts (30% yield) of (C HP=NP(C H =NH Cl is recovered. The melting point, infrared and phosphorusNMR spectra are identical with those described in Example 1 and theelemental analysis is in agreement.

EXAMPLE 3 A solution of 31 parts of (C H PNH Cl made according to theprocedure in Step 1 of Example 1, and 22 parts of (C H PCl in 300 partsof chloroform is refluxed under nitrogen for five minutes and thencooled in an ice bath. A cold solution of 20 parts of (C H N in parts ofCHCl is added, followed by 800 parts of CCl.;. The (C H NHCl which formsis filtered in a closed system and found to be a quantitative yield. Thefiltrate is distilled Off to yield a resinous substance. Upon additionof approximately equivalent amounts of acetonitrile and water, crystalsseparate out from the solution. Filtration, followed byrecrystallization from small amounts of acetone gives 30 parts (63%yield) of M.P. 169171 C. The phosphorus NMR spectrum shows two bands ofequal intensity with chemical shifts at 13.6 and 15.4 p.p.m., showingthe existence of two different phosphorus atoms in the molecule. IRspectrum exhibits the characteristic P=N-P- band at 1290 crn.

Analysis.--Calcd. for C H P NO: C, 75.46%; H, 5.28%; N, 2.93%; P,12.97%. Found: C, 75.41%; H, 5.31%; N, 2.96%; P, 12.79.

EXAMPLE 4 In a single-neck, 300 ml. flask, a solution of 54 parts of (CH P=NH Cl, made according to the procedure described above, 50 parts of(C H PCl and 70 parts of (C H N, in 783 parts of acetonitrile, isgradually heated to reflux temperature (about 82 C.) for 1 hr. whilemaintaining anhydrous conditions. On cooling to room temperature, (C HNHCl crystallizes out. After filtering and subsequent extraction withmore acetonitrile, 47 parts of (C H NHCl is recovered. Excess NH is thenpassed through the filtrate and the mixture refluxed again for a fewminutes. On cooling in an ice bath, NH Cl separates and 8.5 parts isrecovered by filtration. The acetonitrile is then distilled off from thefiltrate, leaving a resinous material. The resin is dissolved in hotbenzene and on cooling, 21 parts (32% yield) of crystals separates out.Recrystallization from acetonitrile and ether gives the desired product,

and the hydrolysis product of (C H PCl namely (C H POOH. The -P=NP bandappears at 1230 cm.- and the phosphorus NMR exhibits two peaks at 14.6and 7.6 p.p.m. in a 2/1 ratio.

Analysis.Calcd. for C H P N Cl: C, 74.55%; H, 5.21%; P, 12.01%; N,3.62%; Cl, 4.58%. Found: C, 72.24%; H, 5.41%; P. 11.78%; N, 3.61%; Cl,4.31%.

EXAMPLE 5 The perchlorate salt of the product of Example 4 is preparedby mixing 6.6 parts of the chloride,

dissolved in ethanol with perchloric acid at room temperature. Crystalsimmediately separate and after recrystallization and drying, 5.7 parts(79% yield) of s 5)3 s 5)2= e 5)3 4 M.P. 272-275 C. is recovered. Theinfrared and phosphorus NMR spectra are essentially identical to thoseof the chloride.

Analysis.Calcd. for C4 H40P3N204cl: C, H, 4.81%; P, 11.09%; N, 3.34%;CI, 4.23%. Found: C, 68.80%; H, 4.76%; P, 11.61%; N, 3.32%; CI. 3.98%.

EXAMPLE 6 The process of Example 1, Steps 2 and 3 is repeated with theexception that in Step 2, the product of Example 1 is reacted with adisubstituted pentavalent chlorophosphine. Accordingly, 42 parts of 27parts of (C H PCl 1566 parts of acetonitrile, and 25 parts of (C H N areplaced in the reaction flask as previously described. After refluxingfor about 45 minutes, and cooling to about C., 5 parts of NH is added.Upon filtration, evaporation of the solvent and recrystallization, 31parts (53% yield) of M.P. 2l4-216 C., is obtained. The infrared spectrumexhibits the P-=N--P band at 1250-1300 cm.- and the phosphorus NMRspectrum shows two peaks at 16.2 and -7.2 p.p.m. in a 2/1 ratio.

Analysis.-Calcd. for C42H37P3N3Cli C, H, 5.23%; P, 13.04%; N, 590%; Cl,4.97%. Found: C, 70.68%; H, 5.27%; P, 12.91%; N, 5.94%; CI, 5.30%.

We claim:

1. A process for the preparation of a linear phosphonitrile whichcomprises:

(a) chlorinating with chlorine gas a trisubstituted phosphine having theformula (R) (R (R )P wherein the Rs represent a phenyl or substitutedphenyl radical of the formula (C H ,,)Y where Y represents alkyl of from1 to 6 carbon atoms, alkoxy of from 1 to 6 carbon atoms, perfluoroalkylhaving 1 to 4 carbon atoms, perfluoroalkoxy having 1 to 4 carbon atoms,fluoro, nitro, cyano and n has a value of from 1 to 5, and subsequentlyammoniating with ammonia the chlorinated phosphine to produce atrisubstituted phosphinimide chloride of the formula R(R (R PNH CI,

(b) reacting said phosphinimide chloride with a phosphine selected fromthe group consisting of a disubstituted trivalent and pentavalentchlorophosphine of the formula (R (R*)PC1 wherein the Rs represent aphenyl or substituted phenyl radical of the formula (C H )Y where Yrepresents alkyl of from 1 to 6 carbon atoms, alkoxy of from 1 to 6carbons atoms, perfluoroalkyl having 1 to 4 carbon atoms, fluoro, nitro,cyano and n has a value of from 1 to 5, and m equals 1 or 3, in thepresence of a Lewis base,

(c) ammoniating with ammonia the resulting products to produce a linearphosphonitrile of the formula wherein when n equals 1 or 2, X is anamino radical and when n equals 2, X is a phenyl or substituted phenylradical of the formula (C H )Y where Y represents alkyl of from 1 to 6carbon atoms, alkoxy of from 1 to 6 carbon atoms, perfluoroalkyl having1 to 4 carbon atoms, perfluoroalkoxy having 1 to 4 carbon atoms, fluoro,nitro, cyano and n has a value of from 1 to 5, with the proviso thatwhen m equals 1 in the above formula the reaction product of step (b) ischlorinated prior to ammoniation. 2. The process of claim 1 wherein theRs are phenyl. 3. The process of claim 1 with the additional step ofreacting the resulting linear phosphonitrile of claim 1 of the formulaR[P(R )(R =N]P(R )(R =NH Cl sequentially with a disubstituted trivalentor pentavalent chlorophosphine of the formula (R )(R*)PCI wherein the Rsrepresent a phenyl or substituted phenyl radical of the formula (C,;H,,)Y where Y represents alkyl of from 1 to 6 carbon atoms, alkoxy offrom 1 to 6 carbon atoms, perfluoroalkyl having 1 to 4 carbon atoms,perfluoroalkoxy having 1 to 4 carbon atoms, fluoro, nitro, cyano and nhas a value of from 1 to 5, and m equals 1 or 3, in the presence of aLewis base, and then ammoniating with ammonia the resulting product toproduce a higher molecular weight linear phosphonitrile with the provisothat when m equals 1 in the above formula the reaction product ischlorinated prior to ammoniation.

4. The process of claim 3 wherein the Rs are phenyl.

5. A process for the preparation of a linear phosphonitrilic oxide whichcomprises:

(a) chlorinating with chlorine gas a trisubstituted phosphine having theformula (R) (R (R )P wherein the Rs represent a phenyl or substitutedphenyl radical of the formula (C H ,,)Y where Y represents alkyl of from1 to 6 carbon atoms, alkoxy of from 1 to 6 carbon atoms, perfluoroalkylhaving 1 to 4 carbon atoms, perfluoroalkoxy having 1 to 4 carbon atoms,fluoro, nitro, cyano and n has a value of from 1 to 5, and subsequentlyammoniating with ammonia the chlorinated phosphine to produce a tri- 9substituted phosphinimide chloride of the formula R(R (R )PNH Cl,

(b) reacting said phosphinimide chloride with a phosphine selected fromthe group consisting of a trivalent and pentavalent chlorophosphine ofthe formula (R )(R )PCI wherein the Rs represent a phenyl or substitutedphenyl radical of the 'formula with the proviso that when m equals 1 inthe above formula the reaction product of step (b) is chlorinated priorto hydrolysis. 6. The process of claim 9 wherein the Rs are phenyl. 7.The linear phosphonitrile having the formula wherein R, R R R and Rrepresent a phenyl or substituted phenyl radical, X is an amino radicalof the formula (C H JY Where Y represents alkyl of from 1 to 6 carbonatoms, alkoxy of from 1 to 6 carbon atoms, perfluoroalkyl having 1 to 4carbon atoms, perfluoroalkoxy having 1 to 4 carbon atoms, fluoro, nitro,cyano and n has a value of from 1 to 5, when n is 1 or 2, or X is aphenyl or substituted phenyl radical of the formula (C H )Y where Yrepresents alkyl of from 1 to 6 carbon atoms, alkoxy of from 1 to 6carbon atoms, perfiuoroalkyl having 1 to 4 carbon atoms, perfiuoroalkoxyhaving 1 to 4 carbon atoms, fluoro, nitro, cyano and n has a value offrom 1 to 5, when n is 2.

8. The linear phosphontrile s s 3 s s 2= 2 9. The linear phosphonitrile10. The linear phosphonitrile (C6H5 2 NP s s 3= s s 2= 2 ReferencesCited Appel et a1., Zeitschrift fur Anorg. und Allg. Chemie, vol. 311,pp. 290-301 (September 1961).

Bode et a1. Berichte, vol. 75, pp. 215-21 (1942).

HENRY R. J ILES, Primary Examiner H. I. MOATZ, Assistant Examiner US.Cl. X.R. 25250, 73; 260543.2

f -@3 UNITED STATES PA'EENT GFFKCE CERTIFICATE OF CORRECTION Patent No.3 7,70% Dated September 16, 1969 idmard F. Moran and Donald P. Reider Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

$.- Column 6, line 29, after "atoms," insert -perfluoroalko having 1 t3' carbon atoms,--. Colmnn 1;}, line 2 4, change "9 to -ES-: 29, after"radical" i1l.rst occurrence) delete "X is an amino radical". Column 10,line U, after "1 to 5," insert -X is an amino radical-; ne l'i', theformula should read C-H P=NP 0,-H :NP C,-H.. ,c hH. l-m

b3 3 0 5 2 03L A SPGNED AND SEALED MAY 1 21970 (SEAL) Attest:

WILLIAM 1; JQCjffU .Fl tcher Ir. m l YL JR Edward M e K334551088? ofPatents Attesting Offi

1. A PROCESS FOR THE PREPARATION OF A LINEAR PHOSPHONITRILE WHICHCOMPRISES: (A) CHLORINATING WITH CHLORINE GAS A TRISUBSTITUTED PHOSPHINEHAVING THE FORMULA (R)(R1)(R2)P WHEREIN THE R''S REPRESENT A PHENYL ORSUBSTITUTED PHENYL RADICAL OF THE FORMULA (C6H5-N)YN WHERE Y REPRESENTSALKYL OF FROM 1 TO 6 CARBON ATOMS, ALKOXY OF FROM 1 TO 6 CARBON ATOMS,PERFLURORALKYL HAVING 1 TO 4 CARBON ATOMS, PERFLUOROALKOXY HAVING 1 TO 4CARBON ATOMS, FLUORO, NITRO, CYANO AND N HAS A VALUE OF FROM 1 TO 5 ANDSUBSWQUENTLY AMMONIATING WITH AMMONIA THE CHLORINATED PHOSPHINE TOPRODUCE A TRISUBSTITUTED PHOSPHINIMIDE CHLORIDE OF THE FORMULAR(R1)(R2)PNH2CL, (B) REACTING SAID PHOSPHINIMIDE CHLORIDE WITH APHOSPHINE SELECTED FROM THE GROUP CONSISTING OF A DISUBSTITUTEDTRIVALENT AND PENTAVALENT CHLOROPHOSPHINE OF THE FORMULA (R3)(R4)PCLMWHEREIN THE R''S REPRESENT A PHENYL OR SUBSTITUTED PHENYL RADICAL OF THEFORMULA (C6H5-N)YN WHERE Y REPRESENTS ALKYL OF FROM 1 TO 6 CARBON ATOMS,ALKOXY OF FROM 1 TO 6 CARBON ATOMS, PERFLUOROALKYL HAVING 1 TO 4 CARBONATOMS, FLUORO, NITRO, CYANO AND N HAS A VALUE OF FROM 1 TO 5, AND MEQUALS 1 OR 3, IN THE PRESENCE OF A LEWIS BASE, (C) AMMONIATING WITHAMMONIA THE RESULTING PRODUCTS TO PRODUCE A LINEAR PHOSPHONITRILE OF THEFORMULA